Detergent compositions containing polymeric quaternary ammonium salts



United States Patent US. Cl. 252-106 6 Claims ABSTRACT OF THE DISCLOSUREDetergent compositions containing quaternary ammonium salts ofpolymerized epichlorohydrin are disclosed. These detergent compositionshave effective antibacterial activity.

This application is a continuation-in-part of the copending applicationof George B. Walker and Cushman M. Cambre, Ser. No. 335,665, filed Jan.3, 1964, now Patent No. 3,428,680.

This invention relates to antibacterial quaternary ammonium salts ofpolymerized epichlorohydrin and to a method of preparing the same. Moreparticularly, this invention relates to salts having the followingstructural formula:

wherein R is an aliphatic group containing from 1 to about 24 carbonatoms, R and R" each are aliphatic groups containing from 1 to about 4carbon atoms. R and R" can be different in the same compound. R, R andR" have this definition throughout the description of this invention;they are preferably n-alkyls. n-I-m ranges from 2 to 50; n ranges from 1to 50; in ranges from 0 to 49. n+m+ the number of carbon atoms in R mustbe greater than 12. Preferably n-l-m has a value of 4 to 15, n a valueof 1 to 15 and m a value of 0 to 14. n, m and n-f-m are average valuesby the nature of the reaction forming the polymers; there fore, n, m andn+m can have fractional values.

Antibacterial quaternary ammonium chlorides are known to the art.Antibacterial compounds of the above structural formula, however, arenot.

It is, therefore, an object of this invention to provide polyquaternaryammonium compounds having the above formula which are outstandinglyactive as antibacterial agents.

It is a further object of this invention to prepare such compounds byreacting acyclic tertiary amines with poly epichlorohydrin.

These and other objects will become apparent as the invention ishereafter described in more detail.

Anti-bacterial acyclic polyquaternary ammonium compounds, none of whichare known to be described in the prior art and exemplary of those withinthe present invention, are set forth in Table I below wherein thetertiary amine, m and n are applied in the structural formula set forthabove.

TABLE I Moles epichlorohydrin in polymer=n+mz Acyclic tertiary amine RIN RII 5 Octyldimethyl. 5 Decyldirnethyl. 5 Dodecyldimethyl. 5Dodecyldiethyl. 5 Octadecyldimethyl. 12.5 Trimethyl. 12.5 Triethyl. 12.5Tripropyl. 12.5 Methylethylpropyl. 12.5 Tributyl. 12.5 Hexyldimethyl.12.5 Octyldimethyl. 12.5 Decyldimethyl. 12.5 Dodecyldimethyl. 12.5Dodecyldiethyl. 12.5 Dodecylmethylethyl. 12.5 Dodecylethylbutyl. 12.5Octadecyldimethyl. 12.5 Eicosyldimethyl. 12.5 Docosyldimethyl. 25.0Trimethyl. 25.0 Triethyl. 25.0 Tripropyl. 37.5 Trimethyl. 37.5 Triethyl.37.5 Tripropyl. 37.5 Octadecylmethylbutyl.

In the above table the value of m can be 0, 1 or range up to n-l-m-l.

The preferred compound within the scope of the invention is:

Compounds similar to those of the present invention but with R and/or R"containing more than about 4 carbon atoms apparently cannot be formed ina reasonable amount of time.

The degree of polymerization (n+m) is arbitrarily limited to 50 becauseof difiiculty in producing compounds with n+m greater than 50. If atertiary amine is reacted with epichlorohydrin, the tertiary aminecatalyzes polymerization, and the monomer apparently cannot be formed.If n+m'+ the number of carbon atoms in R is not greater than 12,compounds similar to those of the present invention can be formed.However, such compounds do not have anti-bacterial properties. Thus, foranti-bacterial properties in polymers having a low degree ofpolymerization, a long chain length R is necessary.

The degree of quaternization or 11 must at least be 1. No increase inanti-bacterial eflicacy is apparent over n=1 as the value of n israised. The precise value of m within the above stated ranges is notcritical.

These anti-bacterial acyclic polyquaternary ammonium compounds can beproduced by a variety of methods. It is preferable to start withpolymerized epichlorohydrin. The polymerized epichlorohydrin is reactedwith an acyclic tertiary amine, either in the presence of a solvent orwith no solvent present, together with a suitable quaternizationcatalyst. If a solvent is present, the reaction can be carried out atthe reflux temperature of the solvent.

If no solvent is present, the boiling point of the acyclic; tertiaryamine is the limiting reaction temperature. Mixtures of acyclic tertiaryamines can be employed or different amines meeting the limitationsherein can be added sequentially. GenerallyQreaction temperatures rangefrom 60 F. to 300 F.

Examples of acyclic tertiary amines that can be used to producecompositions within the scope of the present invention aretrimethylamine, triethylamine, tripropylamine, methylethylpropylamine,tributylamine, hexyldimethylamine, octyldimethylamine,decyldimethylamine, dodecyldimethylamine, dodecylmethylethylamine,dodecyldiethylamine, dodecylethylbutylamine, octadecyldimethylamine,octadecylmethylbutylamine, eicosyldimethylamine anddocosyldimethylamine.

The polymerized epichlorohydrin referredto above has the followingstructure:

wherein n-l-m is the degree of polymerization. The -CH Cl group in thepolyepichlorohydrin structure will hereafter be referred to as a pendentchloromethyl group and the Cl atom in the polyepichlorohydrin structureas a pendent chlorine atom.

Examples of catalysts that can be used in a process to produce thecompounds of the present invention are alkaline substances such assodium bicarbonate, sodium hydroxide, potassium bicarbonate, potassiumhydroxide and mixtures of these. The amount of catalyst to be usedranges from 0.1 to 6% by weight of polyepichlorohydrin.

Suitable solvents for such a process include water, acetone, benzene andlower primary alcohols such as methyl, ethyl, propyl, isopropyl, butyland iso-butyl alcohols.

In the preferred method, polyepichlorohydrin, e.g. where n+m=12.5, isrefluxed in aqueous isopropanol in the presence of NaHCO catalyst withsufficient molar quantities of an acyclic tertiary amine, e.g.trimethylamine, to quaternize from 1 to m+n of the pendent chlorineatoms in the pendent chloromethyl groups. This is shown in the followingrepresentative equation:

H-CH CH-Ql DRRRHN Nance.

L lHgCl J i propanol TcH-O CH2'CHO1 H 2 liJHe J t. m it Cln Alsoepichlorohydrin can be refluxed in a solvent such as benzene with anacyclic tertiary amine, e.g. trimethylamine, as a polymerizationcatalyst followed by the quaternization of the polyepichlorohydrin thusformed by the same amine. This is shown in the following representativeequation, e.g. wherein n+m=l2.5:

The following specific examples are illustrative of the presentinvention, but are not limitive thereof:

EXAMPLE I A mixture of parts (0.087 mole) of polyepichlorohydrin with anaverage molecular weight of 1150, equivalent to 12.5 molesepichlorohydrin monomer in the polymer or n+m:l2.5 (Dow Chemical Co.,Polyglycol 166ll50), 78.4 partsof 25% aqueous trimethylamine solution(equivalent to 0.335 mole of anhydrous trimethylamine), and 178.4 partsof isopropyl alcohol, together with 6 parts sodium bicarbonate (6% byweight, based on polyepichlorohydrin) was refluxed for a total of sevenhours. The reaction mixture was cooled to room temperature and NaHCOremoved by filtration. Removal of isopropyl alcohol under aspiratorvacuum yielded a tan waxy material that was completely water soluble andether insoluble. Ionizable chloride content: actual 9.4%; theory, 10.2%;this indicates a high degree of quaternization of 92.0%. The formedcompound had the general structural formula set forth above withn+m=12.5, n=4, and the tertiary amine=trimethylamine; it is eifective asan antibacterial agent.

EXAMPLE II A mixture of 100 parts (0.087 mole) of polyepichlorohydrinsimilar to that used in Example I was refluxed with 33.90 parts (0.335mole) of triethylamine together with 133.9 parts of isopropyl alcoholand 6 parts of sodium bicarbonate for a total of seven hours. Theproduct obtained after removal of the sodium bicarbonate by filtrationat room temperature, and the isopropyl alcohol by evaporation, was alight tan waxy solid that was water soluble and either insoluble. Theionizable chloride content was 8.25% while the theoretical content was9.10%, indicating a quaternization of 90.5%. The formed compound had thegeneral structural formula set forth above with n+m=12.5, 11:4, and thetertiary amine: triethylamine; it is effective as an antl bacterialagent.

EXAMPLE III One hundred parts 0.22 mole) of polyepichlorohydrin (DowChemical Company Polyglycol 166-450, average molecular weight=450,equivalent to 5 moles of epichlorohydrin in the polymer or n+m=5 141parts of dodecyldimethylamine (0.66 mole) and 6 parts of sodiumbicarbonate were heated together under a nitrogen atmosphere for a totaltime of five hours between the temperatures of and C. The reactionmixture was freed from sodium bicarbonate by filtration and was solublein isopropanol and in water but was ether insoluble. Ionizable chloridecontent of 8.25% compared to the theoretical value of 9.75% indicatedthat a quaternization completeness of 84.5% was obtained. The formedcompound had the general structural formula set forth above with n+m=5,n=3 and the tertiary amine=dodecyldimethylamine; it is effective as ananti-bacterial agent.

EXAMPLE IV One hundred parts of polyepichlorohydrin (0.22 mole) as inExample III, 46.86 parts (0.22 mole) dodecyldimethylamine, 147 partsisopropyl alcohol, and 6 parts of sodium bicarbonate were refluxedtogether for seven hours. The product of this reaction was freed fromsodium bicarbonate by filtration when cool and the alcohol was removedunder vacuum. The resulting material was water soluble and etherinsoluble. The ionizable chloride content of 3.58% compared with thetheoretical value of 5.35% indicated that quaternization to the extentof 67% had occurred. The formed compound had the general structuralformula set forth above with n+m=5, n=1 and the tertiaryamine:dodecyldimethylamine; it is effective as an antibacterial agent.

One hundred parts (0.22 mole) of polyepichlorohydrin as in Example III,140.58 parts (0.66 mole) of dodecyldimethylamine (mole ratio amine topolyepichlorohyof these compounds was determined by conducting StandardTube Dilution Tests. Such tests are conducted in vitro and consistessentially of preparing test tubes of a standardized broth mediumcontaining serial dilutions (diminishing concentrations) of a compoundbeing tested,

PillrtS f P PY alcohol and 6 Parts inoculating each tube with apreselected micro-organism Sodlum blcarbonate were refluxed together fora total and after an incubation period, determining the growth of timeof five hours. The polyepichlorohydrm was added b i i each tube in twoportions; one-half at the start of retina and one- Th b th dium employedin th asay tests was an half after two hours had ela sed. After workingup e 10 FDA phenol coefficient test nutrient broth. Stock solu- IeactlonProduct as dfiscnbed 1I1 PTeV1011$ p a'tan tions of the test productwere then prepared in sterile waxy gum WaS btain d that d1 S 1V 1 1 W rf distilled water. Serial dilutions were prepared of the test propanolbut was ether insoluble. The ionizable chloride t ck olution and thenplac d int th tubes containing content of 8.40% lndlcated aquaternization completeness the nutrient broth, of 86%. The formedcompound had the general structural The broth tubes were inoculated witha bacterial susformula set forth abovewith n+rn=5 2:3 and the pensionprepared in the following manner. A 24 hour ternaryamm=dodecyldlmethylamme; 1t 13 effeetlve a broth culture ofgram-positive Staphylococcus aureus an anti-bacterial agent. FDA 209 wasprepared. One-tenth milliliter quantities of the broth culture wereadded per each previously prepared EXAMPLE VI broth tube containing thetest materials. Gram-negative Epichlorohydrin, 115.6 parts (1.25 moles),w dj Escherichia coli ATCC 10536 cultures were prepared as solved in275.6 parts of benzene and the mixture was lnocuhlm 111 a slmllar abrought to th reflux temperature 10 5 parts 05 mole) Treatment tubeswere lncubated for 48 hours at 37 C. of dodecyldimethylamine was addedslowly to the refluxand thfin Observed for f Presence 0r absence ofgrowthing mixture, Aft a t t l reflux ti f 7 h h 25 The smallestconcentratlon of test material completely inproduct was freed frombenzene in a rotary evaporator hibiting growth is theiend Point ThisConcentration (P R under vacuum and th orange waxy id h bt i d permillion of bacteriostatic agent) is called the bacteriowas water solubleand ether insoluble and contained 1.9% static breal point. Appropriatesterility and inoculum conoxirane oxygen compared to the initial valueof 8.3% 0 w r CO P I indicating 77% utilization of the epichlorohydrin.The In order to allow for a comparison or the relative molecular weight(ebullioscopic) was 890 indicating that bacteiostatic effectiveness ofthenovel acyclic polyqnaterapproximately two dodecyldimethylaminemolecules were nary ammonium compounds, slmllar 1n vltro tests wereattached to a polyepichlorohydrin molecule containing run onheterocyclic poly quaternary ammomum comfive monomer units. The formedcompound had the genpounds prepared as shown in W1ttcott, U.S. LettersPatent eral structural formula set forth above with n+m1=5; 2,483,749,granted Feb. 24, 1948. n=2 and the tertiary amine:dodecyldimethylamine;it Such heterocychc compounds were prepared using is an effectiveanti-bacterial agent. pyridine and quinollnetert ary amines.

Efiective agents are also obtained by substituting in the The results ofthe in who tests described above are foregoing examples various otherpreviously described tabulated in Table II.

TABLE II Baeteriostatic breakpoints (parts per million) Gram Gram Molesamine positive negativ- Moles epichlorohydrin in per mole of nncromicrop01yn1er=n+m Tertiary amine p0lymer=n organism organism 2 0.9 1 4 6 20.5 .6 2 1 1 3 5 3 1 3 5 5 1 3 4 15 50 500 6.25 10 25 500 12.5 25 50 5004 1 2 20 OctyldimethyL 4 .s .9 4 6 12. Decyldimethyl. 4 1 2 6 8 12.Dodecyldimethy 4 100 12. do 6.25 25 50 100 12.5 .d0 12.5 25 25 100 5 200.5 12.5 Pyridine a 1,000 1,000 5 Quinoline 3 1, 000 1, 000

1 Staphylococcus aureus FDA 209.

2 Escherichia coli ATCC 10536.

3 Roccal is a registered trademark of an alkyl-dimethyl-benzyl ammoniumchloride wherein the alkyl group is C8 to C15 and is made by SterwinChemicals, Inc., a subsidiary of Sterling Drugs, Inc.

4 These were made according to examples in U.S. 2,483,749.

acyclic tertiary amines for the amines there employed. Similar resultsare also achieved by replacing the solvent and the catalyst of thepreceding examples with other solvents and catalysts of the characterhereinbefore indicated.

EXAMPLE VII As indicated previously, the polyquaternary ammoniumcompounds described herein have been discovered to be valuableanti-bacterial agents. The anti-bacterial activity periorbacteriost-atic properties to the heterocyclic polyquaternary ammoniumcompounds of US. 2,483,749. This is especially true in the case of thepolymers produced by reacting the polye-pichlorohydrin of molecularweight 450 (n+m=) with octyldimethy-lamine, decyldimethylamine anddodecyldimebhyl-amine where the bacteriostatic breakpoints are less than1 ppm. as compared with greater than 1,000 p.p.m. in the case of thequinoline and pyridine compounds made according to US. 2,483,749. Infact, the above-mentioned polymers of the present invention comparefavorably with Roccal, a (Cg-C18) alkyl-di-methyl-benzyl ammoniumchloride made by Sterwin Chemicals, In-c., and which is an efiectivegermicidal agent.

There is thus provided by this invention a class of new compounds whichare effective anti-bacterial agents. These compounds can be dissolved inWater in the range of about 500 to about 1,000 p.p.m. and the solutionused as antibacterial compositions. The water can contain a nonionic orother surfactants if desired.

These new compounds further unexpectedly retain their anti-bacterialproperties when combined with certain detergent compositions. Thus, anefiective anti-bacterial detergent composition can be formulated whichconsists essentially by weight of from about 0.1% to about of an acyclicpolyqu arternary ammonium compound of the present invention, from about5% to about 50% of a compatible detergent selected from the groupconsisting of nonionic, zwitterionic, and ampholytic syntheticdetergents, and from about 5% to about 95% of a builder materialselected from the group consisting of watersoluble inorganic alkalinebuilder salts, Water-soluble organic alkaline sequestrant builder salts,and mixtures thereof. The balance of the detergent composition can bewater, diluents such as sodium sulfate and other compatible additivesand adjuvan-ts. The Weight ratio of detergent active to builder materialin these compositions ranges from about 4:1 to about 1:20.

Water-soluble inorganic alkaline builder salts which can be used in thisinvention alone or in admixture are alkali metal carbonates, borates,phosphates, polyphosphates, bicarbonates and silicates. Ammonium orsubstituted ammonium, e. g., triethanol ammonium, salt-s of thesematerials can also be used. Specific examples of suitable salts aresodium tripolyphosphate, sodium car-bonate, sodium tet-raborate, sodiumand potassium pyrophos phate, sodium and ammonium bicarbonate, potassiumtripolyphosphate, sodium hexaphosphate, sodium sesquicarbonate, sodiumorthophospha-te, and potassium bicarbonate. The preferred inorganicalkaline builders according to this invention are alkali metaltripolyphosphates for built liquid compositions. Potassium is thepreferred alkali metal used in liquid compositions and sodium finds bestapplication for granular ortablet compositions.

Examples of suitable organic alkaline scques-trant builder salts used inthis invention alone or in admixture are alkali met-a1, ammonium orsubstituted ammonium, aminocarboxylates, e.g., sodium and potassiumethylenediaminete-traacet-ate, sodium and potassiumN-(Z-hydroxyethyl)-nitrilodiacetates, sodium and potassium nitrilotriacetates. Mixed salts of these polycanboxylates are also suitable.The alkali metal salts of phytic acid, e.g., sodium phytate are alsosuitable as organic alkaline sequestrant builder salts (see US. Patent2,739,942). Also suitable as organic alkaline sequestrant builder saltsare the water-soluble salts of polycarboxylate polymers and copolymersas described in the copending application of Francis L. Diehl, Ser. No.269,359, filed Apr. 1, 1963, now Patent No. 3,308,067 (e.g., polymers ofitaconic acid, aconit-ic acid, maleic acid, mesaconic acid, turnaricacid, methylene malonic acid, and citracon-ic acid and copolymers withthemselves and other compatible monomers such as ethylene).

Polyphosphates are also valuable builders in terms of g, the presentinvention, including specifically sodium and potassium salts ofethane-l-hydroxy-l,l-diphosphonic acid, sodium and potassium salts ofmethylene diphosphonic acid, and sodium and potassium salts of ethylenediphosphonic acid, and sodium and potassium salts ofethane-l,LZ-triphosphonic acid. Other examples includes the alkali metalsalts of ethane-Z-carboxy-l,l-diphosphonic acid,hydr-oxymethanediphosphonic acid, carbonyldiphosphonic acid,ethane-bhydroxy-Ll,Z-triphosphonic acid,ethane-Z-hydroxy-1,1,2-triphosphonic acid, propane-- 1,1,3,3-tetraphosphonic acid, prop ane- 1 l ,2,3 -tetraphosphonic acid, andpropane-l,2,2,3-tetraphosphonic acid.

Examples of nonionic organic detergents which can be used in thecompositions of this invention are: polyethylene oxide condensates ofalkylphenols wherein the alkylgroup contains from 8 to 15 carbon atoms(e. g., t-octylphenol) and the ethylene oxide is present in a molarratio of ethylene oxide to alkylphenol in the range of 8:1'to 20:1;condensation products of ethylene oxide with the product resulting fromthe reaction of propylene oxide and ethylene diamine wherein themolecular weight of the condensation products ranges from 5,000 to11,000; the condensation products of from about 5 to 30 molesof ethyleneoxide with one mole of a straight or branched chain aliphatic alcoholcontaining from 8 to '18 carbon atoms, e.g., condensation product'of 6moles of ethylene Oxide with one mole of lauryl alcohol; higher alkyldilower alkyl amine or phosphine oxides, e.g., dodecyldimethylamine:oxide or dodecyldimethyl phosphine oxide; alkyl methyl sulfoxides suchas dodecyl methyl sulfoxide.

Ampholytic synthetic detergents can be broadly described as derivativesof aliphatic secondary and tertiary amines in which the aliphaticradical can be straight chain or branched and wherein one of thealiphatic s-ubsti-tuents contains from about 10 to about '20 carbonatoms and one contains an anionic water solubilizing group, e.g.,-carboxy, sulfonate, sultate, phosphate, phosphinate, or phosphonate.Examples of compounds falling Within this definition are sodium3dodecylaminopropion'ate, sodium 3 (N methyl N-hexadecyiamino) -2hydroxypropane-1- sulfona-te and its dodecyl homolog, sodium3-dodecylaminopropane-l-sulfonate, sodium dodecyl-be-ta-alanine, sodiumN-alkyltaurines such as the one prepared by reacting dodecylamine withsodium isethionate according to the teaching of United States lettersPatent No. 2,658,072, N-hig-her alkyl aspartic acids such as thoseproduced according to the teaching of United States Letters Patent No.2,438,091, and the products 'sold under the trade name Miranol anddescribed in United States Letters Patent No. 2,528,378.

Z Witterionic synthetic detergents can be broadly described asderivatives of aliphatic quarternary ammonium phosph-onium, andsulfonium compounds, in which aliphatic radical may be straight chain orbranched, and wherein one of the aliphatic substituents contains fromabout 10 to about 20 carbon atoms and one contains an anionic watersolubilizat-ion group, e.g.', carboxy, sulfonate, sulfate, phosphate,phosphinate, or phosphonate. Examples of compounds falling within thisdefinition are: 3 =(N,Ndimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate and thecorresponding dodecyl 'and tetradecyl homologs and3-(N,N-dimethyl-N-dodecylam momo)apropane-l-sulfonate and thecorresponding hex-adecyl and tetra-decyl homologs.

The compatibility of the acyclic polyquaternary ammonium compounds ofthe present invention with detergent compositions containing theabove-stated amounts of detergent active and alkaline builder is shownin the following example:

EXAMPLE VIII Standard Tube Dilution Tests similar tothose in Example VIIwere conducted; however, 50 p.p.m. of a. detergent compositioncontaining 5% diethanolamide'of coconut oil fatty acid, 7% potassiumtoluene sulfonate,

12% potassium pyrophosphate and 76% water was added to the nutrientbroth. The acyclic olyquaternary ammonium compound tested forcompatibility was one with n+m=5, n=2 and the tertiaryamine=decyldimethylamine. The bacteriostatic breakpoint forStaphylococcus aureus FDA 209 was about 0.6 p.p.m. and for Escherichiacoli ATCC 10536 was less than 5 p.p.m. These breakponits aresubstantially the same as those in Table II where no detergentcomposition was added and such similar results show the compatibility ofthe acyclic polyquaternary ammonium compounds of the present inventionswith detergent compositions containing alkaline builders.

The following examples illustrate heavy-duty detergent compositionswhich contain as antibacterial agents the novel acyclic olyquaternaryammonium compounds of this invention. These compositions can be used,for example, under conditions of ordinary usage to clean soiled clothingand dishes and to inhibit the growth of bacteria on these articles. Allpercentages herein are by weight.

EXAMPLE IX Solid-granules Percent Polyquaternary ammonium compound ofExample I 2 Tallow alcohol ethoxylated with moles of ethylene oxide permole of alcohol Sodium tripolyphosphate 50 Sodium sulfate 33 EXAMPLE XSolid-granules Percent Polyquaternary ammonium compound of ExampleCoconut alcohol (2%-C 66%-C 23%-C 9%- C ethoxylated with 6 moles ofethylene oxide per mole of alcohol 12 Sodium nitrilo triacetate 81EXAMPLE XI Solid-granules Percent Polyquaternary ammonium compound ofExample III 1 Nonylphenol condensed with 12 moles of ethylene oxide permole of phenol Trisodium ethane-l-hydroxy-l,l-diphosphonate 50 Sodiumtripolyphosphate 10 Sodium sulfate 19 EXAMPLE XII Solid-granules 10EXAMPLE XIV Solidgranules Polyquaternary ammonium compound of Example I5 Dimethylcoconut (2%-C 66%-C 23%-C1 9%- C alkylammonia hydroxypropanesulfonate 20 Trisodium ethylidene diphosphonate 30 Sodium sulfate 45Other polyquaternary ammonium salts can be substituted for theolyquaternary ammonium compounds of Examples IX-XV to provide effectiveantibacterial detergent compositions. For example, any of thepolyquaternary ammonium salts in Table I hereinbefore can replace all orpart of the polyquaternary ammonium compounds of the compositions inthese examples. Moreover, other compatible detergents can replace thedetergent actives in the compositions of Examples IX-XV to provideeffective antibacterial detergent compositions. For example, variousampholytic detergents, e.g., dodecyl-betaalanine, the sodium salt ofN-dodecyl taurine, or disodiurn N-dodecyl aspartate can replace all orpart of the amine oxide in Example XIII. Moreover, other builders can besubstituted for the builders of Examples IX-XV to provide effectiveantibacterial detergent compositions. For example, the followingbuilders can be substituted for all or part of those employed in theexamples: sodium ethylenediaminetetraacetate; sodium N-(2-hydroxyethyl)-nitrilodiacetates; phytates; polycarboxylate polymers; otherpolyphosphonates.

The olyquaternary ammonium compounds of the present invention arefurther useful as antistatic agents, emulsifying agents and dispersingassistants.

The foregoing description of the invention has been presented describingcertain operable and preferred embodiments. It is not intended that theinvention should be so limited since variations and modificationsthereof will be obvious to those skilled in the art, all of which arewithin the spirit and scope of the invention.

What is claimed is:

1. An antibacterial detergent composition consisting essentially of fromabout 5% to about 50% of a detergent selected from the group consistingof nonionic, zwitterionic, and ampholytic synthetic detergents, fromabout 5% to about of a builder material selected from the groupconsisting of water-soluble inorganic alkaline builder salts,water-soluble organic alkaline sequestrant builder salts, and mixturesthereof, and from about 0.1% to about 10% of a polyquaternary ammoniumsalt having the following unit structure:

wherein R is an alkyl group having 1 to 24 carbon atoms, R and R" areeach alkyl groups containing from 1 to 4 carbon atoms, n plus m rangesfrom 2 to 50, m ranges from 0 to 49, and n ranges from 1 to 50 andwherein n plus in plus the number of carbon atoms in R is greater than12.

2. The antibacterial detergent composition according to claim 1 whereinthe polyquaternary ammonium salt has a unit structure wherein R is anoctyl group, R and R are each methyl groups, and it plus m is equal to5.

3; The antibacterial detergent composition according to claim 1 whereinthe polyquaternary ammonium salt has a unit structure wherein R is anoctyl group, R and R" are each methyl groups, and n plus m is equal to12.5.

4. The antibacterial detergent composition according to claim 1 whereinthe polyquaternary ammonium salt has a unit structure wherein R is adecyl group, R and R" are each methyl groups, and it plus m has a valueranging from 4 to 15.

5. The antibacterial detergent composition according to'claim 1 whereinthe polyquaternary ammonium salt has a unit structure wherein R is adodecyl group, R

, I "12 and R" are each methyl groups, and 11 plus m has a value rangingfrom 4 to 15.

6. The antibacterial detergent composition according to claim 4 whereinthe polyquatcrnary ammonium salt has a unit structure wherein R is adecyl group, R and R are each methyl groups, n is equal to 2 and m isequal to 3. c

References Cited FOREIGN PATENTS 213,383 2/1961 Austria.

LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner US.Cl. X.R.

